Reaction product of starch with glycol - alkylolamine condensates for the sizing of textile warp strands



Patentecl Oct. 14-, 1952 REACTION PRODUCT OF STARCH WITH GLYCOL ALKYLOLAMINE CONDENQ sA'rEs FOR THE SIZING or TEXTILE WARP STRANDS Bernhard G. Zimmerman, Guilford College, N. C.

,No Drawing- Application February 17, 1949,

Serial No. 77,074

7 Cla ms.

The present invention relates to an organicv reaction product adapted for use in the textile industry for the sizing of warp yarns. threads or strands and to a method of making the said product. More particularly, the invention relates to a reaction product involving condensation together with polymerization in some instances by the reaction of higher glycols, particularly those having at least three carbon atoms in the molecule and in which the hydroxyl groups are in juxtaposition or adjacent each other, with alkylolamines, the said reaction product being combined with starch or a starch product in the manner hereinafter explained, and to a method by which the said reaction product may be readily produced and combined with starch or a starch product.

It is Well known that in the textile industry, various compounds and materials have been employed for the sizing of cotton warp threads or yarns in order to reduce the amount of dust, lint or fibers given off or expelled into the .air during the weaving operation and also in order to serve as lubrication to reduce friction in parts of the loom during the operation thereof. In the weaving operation, the warp threads or yarns are drawn ofi from a warp beam over a whip roll and through tensioning devices before passing to the harness which guides the warp threads or yarns in the loom. In the shedding operation, by which a passageway is formed for the shuttle between separated threads or yarns of the warp, a considerable amount of friction or resistance to separation is developed, which if substantially reduced correspondingly increases the efficiency of the weaving operation.

Among the lubricants or sizing materials which have heretofore been employed for the treatment of cotton warp threads or yarns are tallow, mineral oils, gums, starch, dextrine, esters and other materials which operate separately or combined in some instances to lubricate the Warp strands or to reduce the dusting efiect during the passage of the warp strands through the loom. The results obtained by the use of the various materials heretofore employedhave not'been entirely satisfactory and extensive eiforts have been made in attempts to improve the sizing materials and the operation thereof.

The present invention is based on the discovery that glycols having at least three carbon atoms in the molecule and having their hydroxyl groups in juxtaposition, or adjacent to each other, are more reactive than other glycols'having the same number of carbon atoms in the molecule but in which the hydroxyl groups are not adjacent and react more readily with other components, hereinafter described to form a reaction product which in combination with starch or a starch product is more effective as a sizing compound for cotton warp strands to prevent dusting and to increase weaving efficiency than any of the other compounds or substances heretofore known or used for the purpose.

The reaction of the glycol or glycol admixture with dialkylolamines, in accordance with the method of the invention, is generally carried out at a temperature of from about C. to 250 C., the reaction being carried on for a time surficient for condensation or polymerization, or both, to take place, which in general requires from about four to twenty hours, the resulting product being a thick viscous liquid, which when combined with starch in the manner hereinafter described and applied to warp strands as a coating forms a smooth and tough film upon drying.

One of the objects of the present invention is to provide a new composition of matter or. reaction product adapted to be applied as a sizing to cotton warp threads or yarns to produce a smoother, more durable and more flexible film than that provided by the various sizing materials and compositions heretofore employed.

Another object of the invention is to provide a new product for the sizing of warp strands adapted to improve the weaving efficiency in a loom and which is' adapted to reduce the dusting effect produced during the weaving operation.

Another object of the invention is to provide a new reaction product or composition of matter which is adapted for the sizing of warp strands by which the productive capacity of the loom to be used is substantially increased in the weaving operation.

Another object of theinvention is to provide a.

new reaction product for the sizing of cotton warp strands through the condensation or polymerization of an alkylene glycol, having at-least three carbon atoms in the molecule and in which the hydroxyl groups are in juxtaposition or adjacent to each other, with an alkylolamine, which when combined with starch or a starch product in the manner to be described serves to produce a tough film-formingmaterial.

Another object of the invention is to provide a method for the production of a new and useful organic reaction product combined with starch or a starch product, which is particularly adapt- 3 ed as a sizing medium for warp strands to produce a tough and elastic film thereon.

With these and other objects in view, the invention comprises the various features hereinafter described and particularly defined in the claims annexed hereto.

In carrying out the invention, an alkylene glycol, such as propylene glycol (1,2-propanediol) is reacted with a dialkylolamine, such as diethanolamine, preferably in the presence of a catalyzer, such as potassium acetate, at a temperature at which condensation or polymerization takes place, such as from about 200 C. to 220 C. under atmospheric pressures, the reaction being carried out for a period of from about four to twenty hours and the water formed in the reaction being distilled ofi. The resulting product is a thick viscous liquid which is then combined with starch or a starch product in the manner hereinafter described, whereby when the resulting product is applied to warp strands, such as cotton warp threads, forms a smooth, tough and elastic film after drying.

More specifically, the method of the invention may be carried out by the use of 400 parts by weight of propylene glycol with 200 parts by weight of diethanolamine and 2 parts by weight of potassium acetate, the ingredients being charged into a suitable reaction vessel provided with a condenser and heated to a temperature of about 220 C., the reaction being carried on for a period of about ten hours, during which time a condensation-polymerization reaction takes place, and the water produced in the reaction is permitted to distill off. The reaction may be terminated when the required amount of water has been distilled from the reaction mixture. The product of the reaction is then combined with starch by the use of four parts by weight of the condensation polymer with 400 parts by weight of starch, the admixture being combined by the use of live steam and boiling until the reaction is completed, which may be determined by the hardness and flexibility of the film produced when employing a standard film test. The resulting product when completed as shown by the film test may be used directly, or it may be mixed with other suitable modifying agents, such as tallow, gums, preservatives, antioxidants, antimildew agents or other additives as may be required.

As another example of the mode of carrying out the invention, parts by weight of 1,2- pentanediol (CH3.CH2.CH2.CHOH.CH2OH) which has a boiling point of about 212 C. at atmospheric pressure, may be treated with 50 parts by weight of diethanolamine, the admixture being boiled together for a suiiicient time for the reaction of condensation and polymerization to take place and until the required amount of water has been distilled off. The reaction product may then be combined with starch or a starch product in substantially the same proportions and in the same manner as described in connection with the above specific example of the manner of carrying out the invention. The final product when applied in a thin coating upon cotton warp threads forms, upon drying, a tough and elastic film which serves to greatly reduce dusting in the weaving operation in a loom and substantially increases the loom efficiency. It will be understood that in carrying out the invention in accordance with this example, the

isomer, 2,3pentanediol, in which the hydroxyl groups are also in the adjacent position, may be used in place of 1,2-pentanediol, and the final product will be found to have substantially the same sizing properties, although the boiling point of the 2,3-isomer is somewhat lower (137 C.) than that of the 1,2-compound.

The method of the invention as above described in connection with 1,2-pentanediol and 2,3-pentanediol, may also be carried out in a sim ilar manner by the use of 1,2-butanediol and its isomer, 2,3-butanediol, by which products suitable for the sizing of cotton warp strands with substantially improved efficiency of the loom in which it is used is obtained. The boiling point of the 1,2-butanediol is 192 C. whereas that of the isomer 2,3- is 184 C.

A further example of the mode of carrying out the invention may be illustrated by the reaction of 2,3-hexanediol with a dialkylolamine, the reaction of condensation and polymerization being carried out at a temperature of substantially 220 C. The polymerization product is then combined with starch in the same manner as described in connection with the propylene glycol reaction product and the resulting product may then be admixed with suitable modifying agents, if desired, such as tallow, gums, waxes and other agents to provide any special properties which may be required under varying conditions. The reaction of the glycol with the dialkylolamine is preferably carried out by the use of about 10 parts by weight of 2,3-hexanediol, which has a boiling point of about 207 C. with about 5 parts of diethanolamine, the reaction being carried out at boiling temperature in the same manner as above described in other examples, until a test indicates that the condensation and polymerization reaction is substantially complete. About two parts by weight of the polymerized product is then added to about 200 parts by weight of starch, 11 parts by weight of tallow and about 1250 parts by weight of water, the components being heated in a suitable vessel provided with an inlet for live steam, the reaction being carried on until the starch has been completely plasticized. The resulting product is then made up to a volume of about 200 gallons, if the parts by weight are in pounds. The final product when used for the sizing of warp strands, as cotton warp, by means of the slasher, or machine for applying size to the warp strands, produces upon drying a tough and elastic film which greatly improves the weaving operation.

In place of 2,3-hexanediol in the above example, the isomer, 3,4-hexanediol, which has a boiling point of about 230 C. may be used, but the condensation and polymerization with diethanolamine takes place at a somewhat higher temperature than with the lower boiling isomer.

If desired, a mixture of two or more glycols having at least three carbon atoms in the molecule and the hydroxyl groups in juxtaposition or in the adjacent position may be used in the condensation and polymerization reaction above described, which when combined with starch or a starch product in the manner described produces similar results to those obtained by the use of a single glycol in the reaction.

As above explained, the higher glycols having their hydroxyl groups in juxtaposition or in the adjacent position are found to be better adapted for the condensation or polymerization reaction above described than glycols having their hydroxyl groups separated or at the ends of the molecule with a chain of carbon atoms between the hydroxyl groups. The reason or theory of operation to account for the improved results is not clear or definitely known, but it appears that the higher homologues of glycol with a chain or four or five, or more, carbon atoms between the hydroxyl groups have a tendency to form a closed chain of carbon atoms with one oxygen atom similar to anhydrides, which compound is substantially stable, so that it does not lend itself to the formation of addition products or reaction products involving condensation or polymerization.

In connection with the above description, it will be understood that glycols of higher molecular weight than those specifically referred to may be employed in the reaction as described. The lower gly-cols are generally obtainable on the market, but the higher glycols if not available may be readily prepared in known manner, as by the reaction of the corresponding halogen compounds with a silver salt, as silver acetate, for example, by which the corresponding glycol diacetate is formed, which on heating with water produces the corresponding glycol. Higher glycols of the type R.CHOH.CHOH.R, in which R represents an alkyl radical, and in which the CHOH- groups are directly adjacent, are formed from olefines, either through the medium of their bromine addition products, or by the direct addition of two hydroxyl groups by means of oxidation, as with potassium permanganate, for example. Glycols of this type may also be formed by the reduction of ketones, as by means of electrolysis, which method for the production of glycols with their hydroxyl groups adjacent is also well known and forms no part of the present invention.

The reaction products produced by the method of the invention above described may include preservatives, antioxidants, antimildew agents and other additives to provide the desired viscosity, keeping properties, and resistanceto oxidation and other requirements to be met depending on the particular conditions to be met in any specialized use. As a preservative, which operates without modifying the properties desired in sizing, in the reaction product of the invention, may be mentioned benzoic acid, dimethylglycol, glycerin, propyleneglycol, tannic acid, acetic acid, salicylates, thymol (isopropylmetacresol), beta-naphthol and others. Among the antioxidants or age-resistors which may be used are tannic acid and aniline, although a large variety of chemical substances are available and suitable in the reaction product of the invention which will not interfere with the sizing operation or the application of the reaction product to the warp strands to be treated. As an antimildew agent or mildew preventive, to prevent the growth of parasitic fungi and stain production on the warp threads or yarns, phenols, cresols, and benzoic acid may be used. It will be noted that tannic acid operates both as a preservative and as an antioxidant. Benzoic acid may also have a dual function, serving as a preservative in the composition and as a mildew preventive.

In the use of the product of the first example above described, 100 parts by weight of the reaction product of the example may be combined with parts of propylene glycol, 30 parts of wax, such as ceresin or carnauba wax, 6 parts of gum, as gum Acacia, 3 parts of tannic acid and 1 part of benzoic acid, the parts referred to being in each instance parts by weight. In this composition, the propylene glycol serves not only as a preservative, but as a solvent for the wax and gum present in the composition.

It will be understood that various changes or modifications may be made in the method of the invention and the reaction product thereof as will be apparent to those skilled in the art without departing from the spirit or scope of the invention as defined by the claims annexed hereto.

Having thus described the invention, what is claimed as new is:

1. A reaction product for the sizing of textile warp strands to substantially increase weaving efiiciency and to prevent substantial dusting which comprises the product formed by reacting a glycol having at least three carbon atoms in the molecule and having the hydroxyl groups thereof adjacent to each other in ,the carbon chain with diethanolamine at a temperature of from C. to 250 C. and for a reaction period of from four to twenty hours, said reaction prodnot being combined with starch in the presence of steam to form a viscous liquid reaction product adapted to dry when applied to warp strands in a tough elastic film.

2. A reaction product for the sizing of textile warp strands to substantially increase weaving efilciency and to prevent substantial dusting which comprises the reaction product formed by reacting 1,2-propanediol with diethanolamine at a temperature of from 150 to 250 C. to produce a condensation reaction and for a suflicient reaction period to convert the components to a condensed reaction product, which after removal of water is reacted with starch at an elevated temperature, forming a viscous liquid reaction product adapted to dry when applied to warp strands in a tough elastic film.

3. A method for forming a reaction product for the sizing of textile warp strands which comprises reacting an alkylene glycol having the hydroxyl groups thereof in juxtaposition with an aliphatic alkylolamine at a temperature of from 150 to 250 C. and for a sufficient time to form a condensation product and combining the condensation product at an elevated temperature with starch to form the final reaction product for use in sizing textile warp strands.

4. A method for forming a reaction product for the sizing of textile warp strands which comprises reacting a glycol having at least three carbon atoms in the molecule and having the hydroxyl groups thereof in juxtaposition with an aliphatic dialkylolamine at a temperatur of from 150 to 250 C. for a sufficient period of time to cause a condensation reaction to take place forming a condensation product and thereafter combining the said condensation product with starch in the presence of steam to form a final reaction product for use in sizing textile warp strands.

5. A method for forming a reaction product for the sizing of textile warp strands which comprises reacting a glycol having at least three carbon atoms in the molecule and having the hydroxyl groups thereof adjacent to each other in the carbon chain with diethanolamine at a temperature of from about 150 C. to 250 C. and for a reaction period of from four to twenty hours, to form a condensation reaction product and combining the said condensation products with starch in the presence of steam to form a final reaction product in the form of a viscous liquid adapted to dry when applied to warp strands in a tough elastic film.

6. A method for forming a reaction product for the sizing of textile warp strands to substantially increase Weaving efiiciency and to prevent substantial dusting which comprises reacting 1,2- propanediol with diethanolamine at a suflicient temperature to produce a condensation reaction and for a suificient reaction period to convert the components to a condensation product, removing water from the condensation product, and reacting the condensation product with starch at a temperature of from 150 to 250 C. to form a Viscous liquid reaction product adapted when dry after application to warp strands to form a tough elastic film.

7. A method for forming a reaction product for the sizing of textile warp strands to substantially increase Weaving efliciency and to prevent substantial dusting which comprises reacting a glycol having more than three carbon atoms in the molecule and having the hydroxyl groups thereof adjacent to each other in the carbon chain with an "aliphatic dialkylolamine in the presence of a catalyzer at a temperature of from 8 to 250 C. and for a suflicient time to produce a condensation product, combining the said condensation product with starch at an elevated temperature in the presence of steam to form a final reaction product and removing water therefrom to form a viscous liquid adapted to dry when applied to warp strands in a tough elastic film.

BERNHARD G. ZIMMERMAN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date Re. 22,963 Monson et a1 Jan. 13, 1948 1,923,178 Ulrich et a1 Aug. 22, 1933 2,147,226 Alquist et al Feb. 14, 1939 2,174,762 Schuette et al. Oct. 3, 1939 2,187,823 Ulrich et a1 Jan. 23, 1940 2,195,194 Ulrich et al Mar. 26, 1940 2,243,630 Houk et a1 May 27, 1941 2,290,880 Katzman et a1 July 28, 1942 2,413,463 Nichols et al Dec. 31, 1946 2,438,855 Kerr et al Mar. 30, 1948 

1. A REACTION PRODUCT OF THE SIZING OF TEXTILE WARP STRANDS TO SUBSTANTIALLY INCREASE WEAVING EFFICIENCY AND TO PREVENT SUBSTANTIAL DUSTING WHICH COMPRISES THE PRODUCT FORMED BY REACTING A GLYCOL HAVING AT LEAST THREE CARBON ATOMS IN THE MOLECULE AND HAVING THE HYDROXYL GROUPS THEREOF ADJACENT TO EACH OTHER IN THE CARBON CHAIN WITH DIETHANOLAMINE AT A TEMPERATURE OF FROM 150* C. TO 250* C. AND FOR A REACTION PERIOD OF FROM FOUR TO TWENTY HOURS, SAID REACTION PRODUCT BEING COMBINE WITH STARCH IN THE PRESENCE OF STEAM TO FORM A VISCOUS LIQUID REACTION PRODUCT ADAPTED TO DRY WHEN APPLIED TO WARP STRANDS IN A TOUGH ELASTIC FILM. 